CN112739653B - Method for producing halide - Google Patents

Method for producing halide Download PDF

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Publication number
CN112739653B
CN112739653B CN201980061920.5A CN201980061920A CN112739653B CN 112739653 B CN112739653 B CN 112739653B CN 201980061920 A CN201980061920 A CN 201980061920A CN 112739653 B CN112739653 B CN 112739653B
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firing
halide
solid electrolyte
firing step
equal
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CN112739653A (en
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久保敬
西尾勇祐
酒井章裕
宫崎晃畅
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
    • C01F17/36—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 halogen being the only anion, e.g. NaYF4
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The disclosed method for producing a halide comprises a firing step in which a mixture containing M is fired in an inert gas atmosphere 2 O 3 、NH 4 X and LiZ. The M contains at least one element selected from Y, lanthanoids, and Sc. And X is at least one element selected from Cl, br, I and F. Z is at least one element selected from Cl, br, I and F.

Description

Method for producing halide
Technical Field
The present disclosure relates to a method of manufacturing a halide.
Background
Patent document 1 discloses a method for producing a halide solid electrolyte.
Prior art documents
Patent document 1: international publication No. 2018/025582
Disclosure of Invention
Problems to be solved by the invention
In the prior art, it has been desired to produce a halide by a method having a high industrial productivity.
Means for solving the problems
A method for producing a halide according to one aspect of the present disclosure includes a firing step of firing a mixed material in which M is mixed in an inert gas atmosphere 2 O 3 、NH 4 X and LiZ, said M comprising at least one element selected from Y, a lanthanide and Sc, said X being at least one element selected from Cl, br, I and F, said Z being at least one element selected from Cl, br, I and F.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present disclosure, a halide can be produced by a method with high industrial productivity.
Drawings
Fig. 1 is a flowchart illustrating an example of the manufacturing method according to embodiment 1.
Fig. 2 is a flowchart showing an example of the manufacturing method in embodiment 1.
Fig. 3 is a flowchart showing an example of the manufacturing method in embodiment 1.
Fig. 4 is a flowchart showing an example of the manufacturing method in embodiment 2.
Fig. 5 is a diagram showing an example of a firing temperature profile in the production method according to embodiment 2.
FIG. 6 is a schematic diagram showing a method of evaluating ion conductivity.
Fig. 7 is a graph showing the evaluation results of ion conductivity by AC impedance measurement.
Detailed Description
Hereinafter, embodiments will be described with reference to the drawings.
(embodiment mode 1)
Fig. 1 is a flowchart showing an example of the manufacturing method in embodiment 1.
The manufacturing method in embodiment 1 includes a firing step S1000.
The firing step S1000 is a step of firing the mixed material in an inert gas atmosphere.
Here, the mixed material to be fired in the firing step S1000 is a mixture of M 2 O 3 、NH 4 X and LiZ.
At this time, M contains at least one element selected from Y (i.e., yttrium), lanthanoids (i.e., at least one element selected from La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, and Lu), and Sc (i.e., scandium).
Further, X is at least one element selected from the group consisting of Cl, br, I and F.
In addition, Z is at least one element selected from the group consisting of Cl, br, I and F.
According to the above technical configuration, the halide can be produced by a method with high industrial productivity (for example, a method capable of mass production at low cost). That is, a halide containing Li (i.e., lithium) and M can be produced by a simple production method (i.e., firing in an inert gas atmosphere) without using a vacuum seal tube or a planetary ball mill. In addition, since the M can be made of cheap M 2 O 3 And NH 4 Since X is simply synthesized, the manufacturing cost can be further reduced.
Further, in the present disclosure, M may be at least one element selected from Y, sm and Gd.
According to the above technical constitution, a halide having a higher ion conductivity can be produced.
Further, in the present disclosure, X may be at least one element selected from Cl, br, and I. In addition, Z may be at least one element selected from Cl, br, and I.
According to the above technical constitution, a halide having a higher ion conductivity can be produced.
For example, in the region of M 2 O 3 、NH 4 Li was prepared by using X and LiX (namely, X represents Z in LiZ described above) 3 MX 6 In the case of (2), as a whole systemThe reaction represented by the following formula (1) occurs.
M 2 O 3 +12NH 4 X+6LiX→2Li 3 MX 6 +12NH 3 +6HX+3H 2 O···(1)
In the firing step S1000, for example, the powder of the mixed material may be put into a container (e.g., a crucible) and fired in a heating furnace. In this case, the mixed material may be kept in a state in which the temperature of the mixed material is raised to a predetermined temperature in an inert gas atmosphere for a predetermined time or more. The firing time may be a time of such a length that composition variation of the fired product due to volatilization of the halide or the like does not occur (that is, ion conductivity of the fired product is not impaired).
As the inert gas, helium, nitrogen, argon, or the like can be used.
After the firing step S1000, the fired material may be taken out of the container (e.g., crucible) and pulverized. At this time, the fired product can be pulverized by a pulverizer (e.g., a mortar, a mixer, or the like).
Further, in the present disclosure, the mixed material may be mixed with NH 4 X, liZ, and 2 O 3 a material in which a part of M is replaced with ' another cation ' (i.e., a cation other than Y, lanthanoid, and Sc) '. This improves the properties (e.g., ion conductivity) of the halide obtained by the production method of the present disclosure. Furthermore, the cationic substitution rate of M by "other cations" may be less than 50mol%. This can provide a halide having a more stable structure.
Further, the mixed material in the present disclosure may be mixed with only M 2 O 3 、NH 4 X and LiZ. Alternatively, the mixed material in this disclosure may be other than M 2 O 3 、NH 4 X and LiZ in addition, M and 2 O 3 、NH 4 x and LiZ are different materials.
In the firing step S1000, the mixed material may be fired at 200 ℃ to 650 ℃.
According to the above techniqueThe structure can make M more than 200 ℃ by setting the sintering temperature 2 O 3 、NH 4 X and LiZ. Further, by setting the firing temperature to 650 ℃ or lower, thermal decomposition of the halide produced by the solid-phase reaction can be suppressed.
In the above formula (1), M may be first caused to be 2 O 3 And NH 4 X is reacted with M 2 O 3 And (4) halogenating. Then, M halogenated can be set 2 O 3 Firing curve for reaction with LiX. In this case, it may be selected to be lower than NH 4 Temperature of sublimation point (or melting point) of X and halogenated M 2 O 3 Temperature at which reaction with LiX proceeds (= formation of halide solid electrolyte Li) 3 MX 6 Temperature (c) as a firing temperature.
For example, in the field of the chemical synthesis of 2 O 3 、NH 4 Synthesis of Li with Cl and LiBr 3 YBr 3 Cl 3 In the case of (3), the reaction of the following formula (2) is carried out.
Y 2 O 3 +12NH 4 Cl+6LiBr→2Li 3 YBr 3 Cl 3 +12NH 3 +3HBr+3HCl+3H 2 O …(2)
For example, the firing temperature in this reaction may be set to about 300 ℃ (that is, lower than NH) 4 A sublimation point of Cl (i.e., 335 ℃ C.), and generation of Li 3 YBr 3 Cl 3 Temperature of (d). To produce a halide with higher ionic conductivity, firing may be carried out at a temperature above 300 ℃. In such a case, as shown in embodiment 2 described later, the firing step is set to at least two stages, and the firing temperature in the first-stage firing step is set to be lower than NH 4 The sublimation point of X, and the firing temperature in the firing step after the second stage may be further increased.
In the firing step S1000, the mixed material may be fired for 1 hour to 72 hours.
According to the above technical constitution, a halide having a higher ionic conductivity can be produced by an industrially high-productivity method. That is, by setting the firing time toSetting M to be more than 1 hour, and enabling M to be 2 O 3 、NH 4 X and LiZ reacted well. Further, by setting the firing time to 72 hours or less, volatilization of the halide as the fired product can be suppressed, and a halide having a desired composition ratio of the constituent elements can be obtained (that is, variation in composition can be suppressed). This can further improve the ionic conductivity of the halide as a burned product. Namely, for example, a solid electrolyte capable of obtaining a halide of higher quality.
Fig. 2 is a flowchart showing an example of the manufacturing method in embodiment 1.
As shown in fig. 2, the manufacturing method in embodiment 1 may further include a mixing step S1100.
The mixing step S1100 is performed before the firing step S1000.
The mixing step S1100 is performed by mixing M as a raw material 2 O 3 、NH 4 And a step of mixing X and LiZ to obtain a mixed material (i.e., a material to be fired in the firing step S1000).
As a method for mixing the raw materials, a method using a generally known mixing device (for example, a mortar, a stirrer, a ball mill, etc.) can be used. For example, in the mixing step S1100, powders of the respective raw materials may be prepared and mixed. In this case, in the firing step S1000, the powdery mixture may be fired. The powdery mixture obtained in the mixing step S1100 may be formed into pellets by uniaxial pressing. At this time, in the firing step S1000, the granulated mixture is fired to produce a halide.
In the mixing step S1100, M may be excluded 2 O 3 、NH 4 X and LiZ in addition to M 2 O 3 、NH 4 X and LiZ to give a mixed material.
In the mixing step S1100, the term "M" may be used 2 O 3 Raw material containing mainly "NH 4 The raw material containing X as the main component and the "raw material containing LiZ as the main component" were mixed to obtain a mixed material.
In the mixing step S1100, M may be added 2 O 3 、NH 4 X and LiZ were weighed and mixed in the desired molar ratio, M was adjusted 2 O 3 、NH 4 Mixed molar ratio of X and LiZ.
For example, Y may be 2 O 3 、NH 4 Cl and LiCl as Y 2 O 3 :NH 4 Cl: liCl = 1. Thereby, li having a composition of Li can be produced 3 YCl 6 The compound of (1).
Further, M may be adjusted in advance in consideration of the composition change in the firing step S1000 2 O 3 、NH 4 X and LiZ to offset compositional variation.
Further, in order to stably proceed the synthesis reaction in the firing step S1000, M may be replaced by M 2 O 3 Excess mixing of NH 4 And (4) X. For example, NH 4 X is relative to M 2 O 3 The amount of the surfactant may be 5 to 15mol% more than the stoichiometric ratio.
Fig. 3 is a flowchart showing an example of the manufacturing method in embodiment 1.
As shown in fig. 3, the manufacturing method in embodiment 1 may further include a preparation step S1200.
The preparation step S1200 is a step performed before the mixing step S1100.
The preparation step S1200 is a preparation M 2 O 3 、NH 4 Raw materials such as X and LiZ (i.e., materials mixed in the mixing step S1100).
In the preparation step S1200, M can be obtained by performing material synthesis 2 O 3 、NH 4 X and LiZ. Alternatively, in the preparation step S1200, a generally known commercially available product (for example, a material having a purity of 99% or more) can be used. Further, as the raw material, a dried material may be used. In addition, as the raw material, a crystalline, massive, flaky, powdery, or the like raw material can be used. In the preparation step S1200, a raw material in a crystalline form, a bulk form, or a flake form may be pulverized to obtain a powdery raw material.
Further, the halide produced by the production method of the present disclosure can be used as a solid electrolyte material. In this case, the solid electrolyte material may be, for example, a lithium ion conductive solid electrolyte. In this case, the solid electrolyte material can be used, for example, as a solid electrolyte material used for an all-solid lithium secondary battery.
(embodiment mode 2)
Embodiment 2 will be described below. The description overlapping with embodiment 1 above is appropriately omitted.
Fig. 4 is a flowchart showing an example of the manufacturing method in embodiment 2.
The production method according to embodiment 2 has the following features in addition to the features of the production method according to embodiment 1.
That is, in the manufacturing method of embodiment 2, the firing step S1000 includes the 1 st firing step S1001 and the 2 nd firing step S1002.
The 2 nd firing step S1002 is a step performed after the 1 st firing step S1001.
In the 1 st firing step S1001, the mixed material is fired at the 1 st firing temperature T1.
In the 2 nd firing step S1002, the mixed material is fired at the 2 nd firing temperature T2.
At this time, T1 < T2 is satisfied.
According to the above technical constitution, a halide having a higher ionic conductivity can be produced by an industrially high-productivity method. That is, M is fired at the 1 st firing temperature T1 2 O 3 And NH 4 After X has reacted (i.e., reacting M) 2 O 3 After halogenation), the halogenated M 2 O 3 And LiZ by firing at the 2 nd firing temperature T2 which is a higher temperature, the crystallinity of the halide as a fired product can be further improved. This can improve the ionic conductivity of the halide as a burned product. Namely, a solid electrolyte capable of producing a halide of good quality, for example.
In the production method of embodiment 2, when X contains Cl (e.g., NH) 4 X is NH 4 Cl), the temperature can meet the condition that T1 is more than or equal to 200 ℃ and less than 330 ℃.
According to the above technical constitution, a halide having a higher ionic conductivity can be produced by an industrially high-productivity method. That is, M can be controlled by setting the 1 st firing temperature T1 to 200 ℃ or higher 2 O 3 And NH 4 X reacts well. Further, NH can be suppressed by setting the 1 st firing temperature T1 to less than 330 ℃ 4 Sublimation of X (e.g. NH) 4 The sublimation point of Cl was 335 deg.C. This can improve the ionic conductivity of the halide as a burned product. Namely, a solid electrolyte capable of producing a halide of good quality, for example.
In the production method of embodiment 2, when X includes Cl (e.g., NH) 4 X is NH 4 Cl), can meet the requirement that T2 is more than or equal to 330 ℃ and less than or equal to 650 ℃.
According to the above technical constitution, a halide having a higher ionic conductivity can be produced by an industrially high-productivity method. That is, the "M" can be adjusted by setting the 2 nd firing temperature T2 to 330 ℃ or higher 2 O 3 And NH 4 The reaction product of X "and LiZ more fully react. This can further improve the crystallinity of the halide as a burned product. Further, by setting the 2 nd firing temperature T2 to 650 ℃ or lower, thermal decomposition of the halide generated by the solid-phase reaction can be suppressed. This can improve the ionic conductivity of the halide as a burned product. Namely, a solid electrolyte capable of producing a halide of good quality, for example.
In the production method of embodiment 2, when X contains Br (for example, NH) 4 X is NH 4 Br) and can meet the requirement that T1 is more than or equal to 200 ℃ and less than 390 ℃.
According to the above technical constitution, a halide having a higher ionic conductivity can be produced by an industrially high-productivity method. That is, M can be controlled by setting the 1 st firing temperature T1 to 200 ℃ or higher 2 O 3 And NH 4 X reacts well. Further, NH can be suppressed by setting the 1 st firing temperature T1 to less than 390 ℃ 4 Sublimation of X (e.g. NH) 4 Br has a sublimation point of396 ℃ C.). This can improve the ionic conductivity of the halide as a burned product. Namely, a solid electrolyte capable of producing a halide of good quality, for example.
In the production method of embodiment 2, when X contains Br (for example, NH) 4 X is NH 4 Br) and can meet the requirement that T2 is more than or equal to 390 ℃ and less than or equal to 650 ℃.
According to the above technical constitution, a halide having a higher ionic conductivity can be produced by an industrially high-productivity method. That is, "M" can be controlled by setting the 2 nd firing temperature T2 to 390 ℃ or higher 2 O 3 And NH 4 The reaction product of X "and LiZ more fully react. This can improve the crystallinity of the halide as a burned product. Further, by setting the 2 nd firing temperature T2 to 650 ℃ or lower, thermal decomposition of the halide generated by the solid-phase reaction can be suppressed. This can improve the ionic conductivity of the halide as a burned product. Namely, a solid electrolyte capable of producing a halide of good quality, for example.
In the production method of embodiment 2, when X includes I (e.g., NH) 4 X is NH 4 I) can meet the requirement that T1 is more than or equal to 200 ℃ and less than 550 ℃.
According to the above technical constitution, a halide having a higher ionic conductivity can be produced by an industrially high-productivity method. That is, M can be controlled by setting the 1 st firing temperature T1 to 200 ℃ or higher 2 O 3 And NH 4 X reacts more fully. Further, NH can be suppressed by setting the 1 st firing temperature T1 to less than 550 ℃ 4 Sublimation of X (e.g. NH) 4 The sublimation point of I is 551 ℃ C. This can improve the ionic conductivity of the halide as a burned product. Namely, a solid electrolyte capable of producing a halide of good quality, for example.
In the production method of embodiment 2, when X includes I (e.g., NH) 4 X is NH 4 I), T2 is more than or equal to 550 ℃ and less than or equal to 650 ℃.
With the above technical configuration, ions having higher ion density can be produced by a method with high industrial productivityA halide of conductivity. That is, "M" can be controlled by setting the 2 nd firing temperature T2 to 550 ℃ or higher 2 O 3 And NH 4 The reaction product of X "and LiZ more fully react. This can further improve the crystallinity of the halide as a burned product. Further, by setting the 2 nd firing temperature T2 to 650 ℃ or lower, thermal decomposition of the halide generated by the solid-phase reaction can be suppressed. This can improve the ionic conductivity of the halide as a burned product. Namely, for example, a solid electrolyte capable of obtaining a high-quality halide.
In the production method of embodiment 2, when X includes F (e.g., NH) 4 X is NH 4 F), T1 is more than or equal to 200 ℃ and less than 230 ℃.
According to the above technical constitution, a halide having a higher ionic conductivity can be produced by an industrially high-productivity method. That is, M can be controlled by setting the 1 st firing temperature T1 to 200 ℃ or higher 2 O 3 And NH 4 X reacts well. Further, NH can be suppressed by setting the 1 st firing temperature T1 to less than 230 ℃ 4 Sublimation of X (e.g. NH) 4 The sublimation point of F was 238 deg.C). This can improve the ionic conductivity of the halide as a burned product. Namely, for example, a solid electrolyte capable of obtaining a high-quality halide.
In the production method of embodiment 2, when X includes F (e.g., NH) 4 X is NH 4 F), T2 is more than or equal to 230 ℃ and less than or equal to 650 ℃.
According to the above technical constitution, a halide having a higher ionic conductivity can be produced by an industrially high-productivity method. That is, "M" can be controlled by setting the 2 nd firing temperature T2 to 230 ℃ or higher 2 O 3 And NH 4 The reaction product of X "and LiZ more fully react. This can further improve the crystallinity of the halide as a burned product. Further, by setting the 2 nd firing temperature T2 to 650 ℃ or lower, thermal decomposition of the halide generated by the solid-phase reaction can be suppressed. This can improve the ionic conductivity of the halide as a burned product. That is, for example, the best can be obtainedA solid electrolyte of a halide of the substance.
Fig. 5 is a diagram showing an example of a firing temperature profile in the production method according to embodiment 2.
As shown in fig. 5, in the 1 st firing step S1001, the mixed material may be fired for the 1 st firing time P1.
In the 2 nd firing step S1002, the mixed material may be fired during the 2 nd firing time P2.
At this time, P1 > P2 can be satisfied.
According to the above technical constitution, a halide having a higher ionic conductivity can be produced by an industrially high-productivity method. That is, M can be fired at the 1 st firing temperature T1 for a longer period of time, that is, during the 1 st firing time P1 2 O 3 And NH 4 X is sufficiently reactive (i.e., capable of rendering M 2 O 3 Fully halogenated). Then, by reacting the fully halogenated M 2 O 3 The halogen compound is fired at LiZ at a 2 nd firing temperature T2, which is a higher temperature, for a 2 nd firing time P2, whereby the crystallinity of the halide compound as the fired product can be further improved. This can improve the ionic conductivity of the halide as a burned product. Namely, for example, a solid electrolyte capable of obtaining a high-quality halide.
The 1 st firing time P1 may be 1 hour or more and 72 hours or less.
According to the above technical constitution, a halide having a higher ionic conductivity can be produced by an industrially high-productivity method. That is, M can be controlled by setting the 1 st firing time P1 to 1 hour or more 2 O 3 And NH 4 X reacts well. Further, by setting the 1 st firing time P1 to 72 hours or less, "M" can be suppressed 2 O 3 And NH 4 The reaction product "of X is volatilized to obtain a halide having a desired composition ratio of the constituent elements (that is, variation in composition can be suppressed). This can further improve the ionic conductivity of the halide as a burned product. Namely, for example, a solid electrolyte capable of obtaining a halide of higher quality.
The 2 nd firing time P2 may be 1 hour or more and 72 hours or less.
According to the above technical constitution, a halide having a higher ionic conductivity can be produced by an industrially high-productivity method. That is, the "M" can be set to 1 hour or more by setting the 2 nd firing time P2 2 O 3 And NH 4 The reaction product of X "and LiZ reacted sufficiently. Further, by setting the 2 nd firing time P2 to 72 hours or less, volatilization of the halide as the fired material can be suppressed, and a halide having a desired composition ratio of the constituent elements can be obtained (that is, variation in composition can be suppressed). This can further improve the ionic conductivity of the halide as a burned product. Namely, for example, a solid electrolyte capable of obtaining a halide of higher quality.
In the 1 st firing step S1001, M may be added 2 O 3 And NH 4 X reaction to synthesize (NH) 4 ) a MX 3+a (0. Ltoreq. A. Ltoreq.3). In addition, in the 2 nd firing step S1002, (NH) generated in the 1 st firing step S1001 may be used 4 ) a MX 3+a Reacted with LiZ to synthesize a halide (i.e., a solid electrolyte).
For example, with respect to the group Y 2 O 3 、NH 4 Synthesis of Li with Cl and LiBr 3 YBr 3 Cl 3 The firing temperature in this case is considered to be about T1=200 ℃ and about T2=500 ℃. In this case, in the 1 st firing step S1001, NH 4 Cl does not sublime with Y 2 O 3 The reaction mainly generates (NH) 4 ) a MX 3+a (a is more than or equal to 0 and less than or equal to 3). Then, in the 2 nd firing step S1002, (NH) is performed by raising the temperature to 500 ℃ 4 ) a MX 3+a By reacting with LiCl, a halide solid electrolyte having good crystallinity can be realized. By the above, a halide solid electrolyte having higher ionic conductivity can be produced.
In the present disclosure, the firing step S1000 may include another firing step in addition to the 1 st firing step S1001 and the 2 nd firing step S1002. That is, the firing step may include three or more steps depending on the type of the raw material (or the number of raw materials).
Examples
Hereinafter, the details of the present disclosure will be described with reference to examples and comparative examples. These are merely examples and do not limit the disclosure.
In the following examples, the halide produced by the production method of the present disclosure was produced and evaluated as a solid electrolyte material.
< example 1 >
(preparation of solid electrolyte Material)
Under the atmosphere of argon with dew point below-60 ℃, Y is added 2 O 3 、NH 4 Cl and LiBr as Y 2 O 3 :NH 4 Molar ratio of Cl to LiBr =1 4 Cl to make it relative to Y 2 O 3 Excess 10 mol%). They were pulverized with an agate mortar and mixed. Then, the crucible was placed in an alumina crucible, set to T1= T2=300 ℃, and kept under a nitrogen atmosphere for 15 hours.
After firing, the mixture was pulverized in an agate mortar to prepare a solid electrolyte material of example 1.
(evaluation of ion conductivity)
Fig. 6 is a schematic diagram showing an evaluation method of ion conductivity.
The press mold 200 is composed of a frame 201 made of electrically insulating polycarbonate, and an upper punch 203 and a lower punch 202 made of electrically conductive stainless steel.
Using the structure shown in fig. 6, the ion conductivity was evaluated by the following method.
A solid electrolyte powder 100, which is a powder of the solid electrolyte material of example 1, was filled in a press-molding die 200 in a dry atmosphere having a dew point of-60 ℃ or lower, and uniaxially pressed at 300MPa to prepare a conductivity cell of example 1.
Lead wires were led out from the upper part 203 and the lower part 202 of the press machine, respectively, in a pressurized state, and connected to a potentiostat (princetonconnected Research, versaSTAT 4) equipped with a frequency response analyzer, and the ionic conductivity at room temperature was measured by electrochemical impedance measurement.
Fig. 7 is a graph showing the evaluation results of the ion conductivity measured by the AC impedance method. FIG. 7 is a Cole-Cole line graph showing the results of the impedance measurement.
In fig. 7, the real part value of the impedance at the measurement point (arrow in fig. 7) where the absolute value of the phase of the complex impedance is the smallest is regarded as the resistance value with respect to ion conduction of the solid electrolyte of example 1. The ionic conductivity was calculated by the following formula (3) using the resistance value of the electrolyte.
σ＝(R SE ×S/t) -1 ···· (3)
Where σ is the ionic conductivity, S is the electrolyte area (the inner diameter of the frame 201 in FIG. 6), and R is SE Is the resistance value of the solid electrolyte in the impedance measurement described above, and t is the thickness of the electrolyte (the thickness of the solid electrolyte powder 100 in fig. 6).
The ionic conductivity of the solid electrolyte material of example 1 measured at 22 ℃ was 8.6X 10 -5 S/cm。
< example 2 >
(preparation of solid electrolyte Material)
Under the atmosphere of argon with dew point below-60 ℃, Y is added 2 O 3 、NH 4 Cl and LiBr as Y 2 O 3 :NH 4 Molar ratio of Cl to LiBr =1 4 Cl to make it relative to Y 2 O 3 10mol% excess over the stoichiometric ratio). They were pulverized with an agate mortar and mixed. Then, the resultant was placed in an alumina crucible, set to T1=200 ℃, and held for 15 hours under a nitrogen atmosphere, and then set to T2=500 ℃, and held for 1 hour under a nitrogen atmosphere.
After firing, the mixture was pulverized in an agate mortar to prepare a solid electrolyte material of example 2.
(evaluation of ion conductivity)
A conductivity cell of example 2 was produced in the same manner as in example 1, and the ion conductivity was measured.
< examples 3 to 5 >
(preparation of solid electrolyte Material)
In examples 3 to 5, the raw material powder was weighed under an argon atmosphere having a dew point of-60 ℃ or lower.
In example 3, Y is 2 O 3 、NH 4 Cl and LiCl as Y 2 O 3 :NH 4 Cl LiCl =1, 13.2.
In example 4, Y is 2 O 3 、NH 4 Br and LiCl as Y 2 O 3 :NH 4 Br LiCl =1, 13.2.
In example 5, Y is 2 O 3 、NH 4 Br and LiBr as Y 2 O 3 :NH 4 Br LiBr =1, 13.2.
Then, the resultant was placed in an alumina crucible, set to T1=200 ℃, and held for 15 hours under a nitrogen atmosphere, and then set to T2=500 ℃, and held for 1 hour under a nitrogen atmosphere.
After firing, the mixture was pulverized in an agate mortar to prepare solid electrolyte materials of examples 3 to 5.
(evaluation of ion conductivity)
Conductivity measuring cells of examples 3 to 5 were produced in the same manner as in example 1, and the ion conductivity was measured.
< examples 6 to 8 >
(preparation of solid electrolyte Material)
In examples 6 to 8, the raw material powder was weighed under an argon atmosphere having a dew point of-60 ℃ or lower.
In example 6, sm is 2 O 3 、NH 4 Br and LiI as Sm 2 O 3 :NH 4 Br: liI = 1.
In example 7, gd 2 O 3 、NH 4 Br and LiCl with Gd 2 O 3 :NH 4 Br LiCl =1, 13.2.
In example 8, gd 2 O 3 、NH 4 Br and LiBr with Gd 2 O 3 :NH 4 Br LiBr =1, 13.2.
Then, the resultant was placed in an alumina crucible, set to T1=200 ℃, and held for 15 hours under a nitrogen atmosphere, and then set to T2=500 ℃, and held for 1 hour under a nitrogen atmosphere.
After firing, the mixture was pulverized in an agate mortar to prepare solid electrolyte materials of examples 6 to 8.
(evaluation of ion conductivity)
Conductivity measurement cells of examples 6 to 8 were produced in the same manner as in example 1, and the ion conductivity was measured.
< examples 9 and 10 >
(preparation of solid electrolyte Material)
Under the atmosphere of argon with dew point below-60 ℃, Y is added 2 O 3 、NH 4 Cl and LiBr as Y 2 O 3 :NH 4 Cl to LiBr =1, 13.2. They were pulverized with an agate mortar and mixed.
In example 9, the crucible was placed in an alumina crucible, set to T1= T2=200 ℃, and held for 15 hours under a nitrogen atmosphere.
In example 10, the crucible was placed in an alumina crucible, set to T1= T2=500 ℃, and held for 15 hours under a nitrogen atmosphere.
After firing, the mixture was pulverized in an agate mortar to prepare solid electrolyte materials of examples 9 and 10.
(evaluation of ion conductivity)
Conductivity measuring cells of examples 9 and 10 were produced in the same manner as in example 1, and the ion conductivity was measured.
Table 1 shows the respective configurations and the respective evaluation results of examples 1 to 10.
[ Table 1]
Figure BDA0002986067190000141
< comparative examples 1 to 6 >
(preparation of solid electrolyte Material)
In comparative examples 1 to 6, the raw material powder was weighed under an argon atmosphere having a dew point of-60 ℃ or lower.
In comparative example 1, YCl was added 3 And LiCl as YCl 3 LiCl = 1:3.
In comparative example 2, YCl was added 3 And LiBr in YCl 3 LiBr = 1:3.
In comparative example 3, YBr was added 3 And LiBr with YBr 3 LiBr = 1:3.
In comparative example 4, smBr was added 3 And LiI with SmBr 3 LiI = 1:3.
In comparative example 5, gdBr was added 3 And LiBr at GdBr 3 LiBr = 1:3.
In comparative example 6, gdBr was added 3 And LiI at GdBr 3 LiI = 1:3.
These materials were pulverized and mixed in an agate mortar, and then raw material powders were mixed, pulverized and reacted with each other by mechanochemical milling, thereby producing solid electrolyte materials of comparative examples 1 to 6, respectively.
(evaluation of ion conductivity)
Conductivity measuring cells for comparative examples 1 to 6 were prepared in the same manner as in example 1, and the ion conductivity was measured.
The respective configurations and the respective evaluation results of the comparative examples 1 to 6 are shown in table 2.
[ Table 2]
Figure BDA0002986067190000151
< investigation >)
The solid electrolyte material of example 1 showed solid electrolyte of example 9 and example 10Higher ionic conductivity of the host material. It is considered that in firing at 200 ℃, the temperature is lower than the temperature at which a solid electrolyte having high ionic conductivity is produced, and therefore high ionic conductivity cannot be achieved. On the other hand, it is considered that NH is generated during firing at 500 ℃ 4 Cl sublimates, and thus a target solid electrolyte is not generated.
As in the solid electrolyte material of example 2, by setting the firing process to 2 stages and making T1 < T2, higher ion conductivity was achieved.
As in examples 3 to 8, high ion conductivity was achieved both in the case of using Sm and/or Gd as M and in the case of using a plurality of halogens as X and Z.
Examples 1 to 8 showed ion conductivities equivalent to those of the solid electrolyte materials synthesized by the mechanochemical polishing reaction in comparative examples 1 to 6.
As can be seen from the above, the solid electrolyte material synthesized by the production method of the present disclosure exhibits high lithium ion conductivity. The production method of the present disclosure is a simple method and has high industrial productivity. In addition, the manufacturing method of the present disclosure can be made of inexpensive M 2 O 3 And NH 4 Since X is synthesized simply by a solid-phase reaction, the production cost can be further reduced.
Industrial applicability
The production method of the present disclosure is useful, for example, for a production method of a solid electrolyte material. The solid electrolyte material produced by the production method of the present disclosure can be used, for example, in an all-solid lithium secondary battery or the like.
Description of the reference numerals
100. Solid electrolyte powder
200. Pressure forming die
201. Frame structure
202. Lower part of punch press
203. Upper part of the punch press

Claims (12)

1. A process for the production of a halide compound,
comprises a firing step of firing the mixed material in an inert gas atmosphere,
the mixed material is mixed with M 2 O 3 、NH 4 X and LiZ,
said M comprising at least one element selected from the group consisting of Y, lanthanides and Sc,
x is at least one element selected from the group consisting of Cl, br, I and F,
z is at least one element selected from Cl, br, I and F,
in the firing step, the mixed material is fired at 200 ℃ to 650 ℃.
2. The manufacturing method according to claim 1, wherein the substrate is a glass substrate,
in the firing step, the mixed material is fired for 1 hour to 72 hours.
3. The manufacturing method according to claim 1, wherein the substrate is a glass substrate,
the firing step includes a 1 st firing step and a 2 nd firing step performed after the 1 st firing step,
in the 1 st firing step, the mixed material is fired at a 1 st firing temperature T1,
in the 2 nd firing step, the mixed material is fired at a 2 nd firing temperature T2,
t1 < T2.
4. The manufacturing method according to claim 3, wherein the substrate is a glass substrate,
the X comprises a group of atoms selected from the group consisting of Cl,
t1 is more than or equal to 200 ℃ and less than 330 ℃,
t2 is more than or equal to 330 ℃ and less than or equal to 650 ℃.
5. The manufacturing method according to claim 3, wherein the substrate is a glass substrate,
the X comprises Br, and the compound is,
t1 is more than or equal to 200 ℃ and less than 390 ℃,
t2 is more than or equal to 390 ℃ and less than or equal to 650 ℃.
6. The manufacturing method according to claim 3, wherein the substrate is a glass substrate,
the X comprises a group I which is a group I,
t1 is more than or equal to 200 ℃ and less than 550 ℃,
t2 is more than or equal to 550 ℃ and less than or equal to 650 ℃.
7. The manufacturing method according to claim 3, wherein the substrate is a glass substrate,
the X comprises F, and the X is F,
t1 is more than or equal to 200 ℃ and less than 230 ℃,
t2 is more than or equal to 230 ℃ and less than or equal to 650 ℃.
8. The production method according to any one of claims 4 to 7,
in the 1 st firing step, the mixed material is fired for a 1 st firing time P1,
in the 2 nd firing step, the mixed material is fired for the 2 nd firing time P2,
p1 > P2 are satisfied.
9. The manufacturing method according to the above-mentioned claim 8,
the 1 st firing time P1 is 1 hour or more and 72 hours or less.
10. The manufacturing method according to the above-mentioned claim 8,
the 2 nd firing time P2 is 1 hour or more and 72 hours or less.
11. The production method according to any one of claims 1 to 7,
the M is at least one element selected from Y, sm and Gd.
12. The manufacturing method according to claim 1, wherein the substrate is a glass substrate,
x is at least one element selected from the group consisting of Cl, br and I,
and Z is at least one element selected from Cl, br and I.
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